CN1631907A - Method for preparing polymer/inorganic nano composite material powder initiated by nano semiconductor - Google Patents
Method for preparing polymer/inorganic nano composite material powder initiated by nano semiconductor Download PDFInfo
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- CN1631907A CN1631907A CN 200410084568 CN200410084568A CN1631907A CN 1631907 A CN1631907 A CN 1631907A CN 200410084568 CN200410084568 CN 200410084568 CN 200410084568 A CN200410084568 A CN 200410084568A CN 1631907 A CN1631907 A CN 1631907A
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Abstract
The invention belongs to high molecular material technical field, concretely a method to prepare polymer/ inorganic nm compound material powder. The polymerization system compares of: (A) active semi-conductor powder of nm size, (B) free radical monomer containing one or more couple bond, (C) reaction reaction adjusting agent (D) dispersion medium water. The system can make polymerization shot by the ultraviolet ray whose wave length is 300-400nm, then generate the polymer inorganic compound material powder of nm size. In the invention, the synthesizing reaction and material compound are completely in the same time, so it is especially suitable for preparing high molecular compound material with inorganic semi-conductor in it, as well as other compound materials like photovoltaic conversion, plastic procession makeup or coating.
Description
Technical field
The invention belongs to technical field of polymer materials, be a kind of method for preparing the polymer/inorganic nanometer matrix material, be specifically related to a kind of light excitation nano semi-conductor initiated polymerization of using, prepare the method for polymer/inorganic nanometer matrix material.
Background technology
The polymer/inorganic nanometer matrix material is that the inorganic nano structural unit is scattered in the matrix material that forms in the polymeric matrix.Owing to combine the advantage of polymkeric substance and inorganic nano-particle, economical and effectively utilize performances such as the photoelectricity of nanometer uniqueness is pyromagnetic, polymer nanocomposites becomes important novel material.
The preparation method of the polymer/inorganic nanometer matrix material of report has following several at present:
1. parcel polymerization: nanoparticle surface is carried out monomer-grafted or surface treatment, carry out the parcel of polymkeric substance again.U.S. Pat 2002106513 discloses, and at silicon oxide surface grafting active group, is implemented in the nanoparticle surface graftomer by atom transfer radical polymerization.World patent WO0224756 discloses suspension polymerization hydrophobicity clay-polymer composites method.
2. original position method of formation: metal ion or precursor solution are placed segmented copolymer or ionomeric micella, or be dispersed in the polymer phase, again by in-situ reducing or vulcanization reaction, the preparation nanoparticle is dispersed in the matrix material in the polymeric matrix.U.S. Pat 2002055581 discloses emulsion polymerization prepared argillaceous/polymer nanocomposites.
3. template: organically forming the inorganic nano structure in the template, or monomer polymerization in inorganic template obtains the polymer nanocomposite structure.The key issue of template polymerization is the limited polymerization of diffusion, filling and the monomer of monomer in the nanometer space in the nanometer space.
4. intercalation polymeric: monomer and initiator and illiteracy holder soil are mixed the back repolymerization, and representational example is the intercalation composite material that covers holder soil and nylon.Japanese Patent JP2001019854 discloses the preparation method of non-polar polymer resin with the nano intercalated matrix material that covers holder soil.This forwarding method is confined to the inorganic materials of laminate structure.
5. mechanical mixing: after nanoparticle surface handled, with the polymer melt blend.This method is simple, but the reunion that solves nanoparticle is comparatively difficult.Or adopt the grinding plant of high energy that inorganic materials and macromolecular material is compound.
Realize that the gordian technique of polymer/inorganic nanometer matrix material is to solve the bonding force of nanoparticle surface and polymkeric substance.Very weak or when not interacting when the interaction of nanoparticle and polymkeric substance, even formed nanoscale dispersive matrix material, can not embody the effect and the effect of the nanoparticle of being envisioned.
When Nano semiconductor particles is subjected to the UV-irradiation of certain energy, electronics is subjected to exciting transition can take place, thereby generates a pair of photo-generated carrier, promptly has the conduction band electron of reductibility and the valence band hole of oxidisability.The hydroxyl radical free radical that valence band hole and surperficial secondary reaction produce all has the ability that causes radical polymerization.The present invention utilizes the photocatalytic activity of described Nano semiconductor, and the ultraviolet excitation Nano semiconductor produces the electric charge of initiated polymerization, realizes monomer at nano grain surface or nearly surface aggregate, and polyreaction and material are compound to be finished simultaneously.
Summary of the invention
The objective of the invention is to propose the polymkeric substance and the inorganic nano composite powder preparation methods of a kind of nanoparticle and polymkeric substance.
The method for preparing the polymer/inorganic nanometer composite material powder that the present invention proposes is a kind of light polymerization method, concrete steps are to adopt optical radiation exciting light catalytic Nano semiconductor, the trigger monomer polymerization, make monomer in nano grain surface or nearly surf zone polymerization, form the polymer/inorganic nanometer composite material powder.Preparation method of the present invention does not need to add radical initiator.
Among the present invention, polymerization system consisting of by weight:
(1) photocatalytic Nano semiconductor powder 0.01-40%,
(2) Raolical polymerizable monomer 0.01-20%,
(3) reaction control agent 0.01-10%,
(4) dispersion agent: surplus.
Further specifying of reaction system is as follows:
(1) component nanometer photolytic activity semi-conductor powder body material is the material of initiated polymerization, and it can be any semi-conductor with photocatalytic activity.Luminous energy at certain wavelength excites down, and this semiconductor energy produces metastable current carrier (conduction band electron and valence band hole), and can generate free radical by a series of surface reactions.Specifically, it can be but be not limited to following oxide compound: sharp ore deposit type titanium oxide, ferric oxide, silver suboxide, cupric oxide, Tungsten oxide 99.999, zinc oxide, stannic oxide, silicon oxide, cobalt oxide, aluminum oxide, magnesium oxide, fluorine doped tin oxide.Also can be two or more compound of above-mentioned oxide compound.Sharp ore deposit type titanium oxide is preferred.
Among the present invention, the consumption of Nano semiconductor powder A accounts for the 0.01-40% of whole reaction system weight, and preferred range is 0.5%-10%.Term " powder " is meant the exsiccant powdery substance.The median size of Nano semiconductor powder A is 10-100nm, and preferred range is 10-40nm.
(2) reacton of component radical polymerization is the monomer that contains one or more pairs key, and its structural formula is:
Wherein, R
1, R
2, R
3, R
4Identical or different, can be straight chain, side chain or the cyclic saturated hydrocarbyl or the unsaturated alkyl of hydrogen or replacement arbitrarily, also can be amino, alkoxyl group, ketone group, amido or cyano group.This component also should satisfy the requirement of water solubility aspect.
Among the present invention, (20 ℃) can dissolve the 0.1-10 gram to described monomeric water solubility in the water in order to restrain 100.
Among the present invention, described monomeric homopolymer is non-water-soluble.Term " water-insoluble " refers to the polymkeric substance of (20 ℃) solubilized 0-10 gram in 100 gram water here.
Among the present invention, described monomer can be but be not limited to following listed material: methyl acrylate, methyl methacrylate, the pyrroles, aniline, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, vinyl acetate, vinylchlorid, vinylbenzene, α-ethylhexyl, vinyl pyridine, the vinyl benzyl pyrrolidone, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, hydroxypropyl methacrylate, the vinylformic acid hydroxypropyl ester, dimethylaminoethyl methacrylate, the amino propyl ester of dimethylaminoethyl acrylate methyl base, vinylformic acid dimethylamino ethyl ester or vinylformic acid dimethylamino propyl ester.
Among the present invention, monomeric consumption accounts for the 0.01-20% of whole reaction system weight, and suitable consumption is 1-10%.
Among the present invention, reaction control agent, the available compound that contains the variable valence metal ion, said variable valence metal ion can be but be not limited to Cu
2+, Fe
2+, Fe
3+Or Ag
+The consumption of reaction control agent is the 0.01%-10% of total reaction system weight, and scope is 0.1-1% preferably.The effect of reaction control agent is the electronics that capture light excites generation, reduces the recombination probability of hole and electronics, improves the initiation quantum yield in hole, makes monomer be initiated at semiconductor surface, produces monomer free radical and propagating radical.
Dispersion agent, the deionized water of available routine.
In the present invention, except said components, do not need to add initiator and other auxiliary agent.
Among the present invention, light source can be ultraviolet monochromatic ray or the multifrequency light of wavelength in the 300-400 nanometer range.When the ultraviolet multifrequency source that uses wavelength in the 200-400 nanometer range, need to adopt the optical filtering means, get rid of wavelength less than the short wavelength radiation of 300 nanometers.What relatively be fit to is to adopt high voltage mercury lamp, and filters with the copper/saturated copper sulphate aqueous solution.The employing wavelength is that the purpose of 300-400 nanometer irradiation light is in order to prevent that monomer is subjected to irradiation generation auto-polymerization.
Among the present invention, light source can be positioned over the reactor outside or place inside reactor.
Among the present invention, polymerization system just starts ultraviolet source after mixing at least 5 minutes.Like this to guarantee that monomer is in the fully absorption of Nano semiconductor surface.
Polyreaction of the present invention is directly caused by Nano semiconductor, does not need to add initiator.The feature of gained composite powder material is that inorganic nano-particle is aggregated product and wraps up, and has formed the polymer/inorganic composite material powder of nanoscale.The preparation method of polymer/inorganic nanometer matrix material of the present invention, its advantage is that Nano semiconductor participates in polyreaction directly, polyreaction and material are compound to be finished simultaneously, be particularly useful for making the adulterated conductive polymer composite of inorganic semiconductor particle, as the adulterated Pt/Polypyrrole composite material of nano titanium oxide.Method of the present invention also can be applied to prepare the matrix material with photoelectric conversion technique.
According to the present invention, monomer is inorganic semiconductor nanoparticle surface or nearly surf zone polymerization.Its homopolymer of selected monomer is non-water-soluble, and the composite products of generation precipitates when polymerization finishes, so the product separate easily.
The mixture of the present invention's preparation, reality has been carried out surface modification to inorganic nano exactly, has connected high molecular polymer.This strata compound is just as the expanding material between inorganic interface and the macromolecule interfacial, can improve the dispersing property of nanometer inorganic filler in macromolecule matrix greatly, light polymerization method provided by the invention is suitable for preparing the polymer/inorganic nanometer matrix material relevant with plastic processing technology, makeup or coating technology.
Embodiment
Embodiment 1
Take by weighing methyl methacrylate monomer, add deionized water to scale, compound concentration is the monomer solution of 12 grams per liters.Nano titanium oxide (sharp ore deposit type) powder is added in the methyl methacrylate aqueous solution, and the dispersion concentration of titanium dioxide is 1 grams per liter.Add copper nitrate aqueous solution again, make that cupric nitrate concentration is 0.01 mol in the reaction system.Disperseed 10 minutes with ultrasonic continuous, make the nano particle homodisperse.Above-mentioned reaction solution is added in the reactor, stir after 10 minutes, open the high voltage mercury lamp that places reactor outer, the logical copper/saturated copper sulphate aqueous solution circulates in the reactor jacket.In the reactor center position, the yield of radiation of 365 nano wave lengths is 12mw/cm
2Polyreaction continues 300 minutes.
Product is the powder precipitation of white, through infrared spectra and nucleus magnetic resonance
13The C spectrum reaches
1The H spectrum analysis is confirmed to contain polymethylmethacrylate in the product.Recording the polymkeric substance yield by thermal weight loss method (TGA) is 80.9%.Arrive with transmission electron microscope observation, the polymkeric substance that titanium dioxide nano-particle is generated wraps up, and polymer layer of thickness is that 30 nanometers-150 nanometer does not wait.
Embodiment 2
The consumption of nano titanium oxide is 0.2 grams per liter, and other condition is identical with embodiment 1 with experimental procedure.Polyase 13 50 minutes.Product is the precipitation powder of white, and the observations of electron microscope is identical with embodiment 1.
Embodiment 3
Prepare pyrroles's aqueous solution of 10 grams per liters, dispersing nanometer titanium dioxide concentration is 1 grams per liter.Other condition is identical with embodiment 1.Reaction times is 280 minutes.Back 30 minutes of reaction beginning promptly has black precipitate to produce.Infrared spectroscopy confirms to contain polypyrrole and titanium dioxide in the product.Electron microscope observation wraps up to the black polypyrrole that nano-titania particle is generated.
Embodiment 4
The vinyl acetate between to for plastic aqueous solution of ester of preparation 15g/L adds reactor, and the concentration of nano titanium oxide is 1g/L, and the reaction times is 210 minutes.Other condition is identical with embodiment 1.The transformation efficiency of vinyl acetate is 62%, and product is the white powder precipitation.Infrared spectroscopy confirms to contain polyvinyl acetate (PVA) and titanium dioxide in the product.
Comparative example 1
Except that not having nano titanium oxide (sharp ore deposit type) powder, other condition is identical with embodiment 1.React after 300 minutes, sediment-free produces.Thermogravimetic analysis (TGA) and super centrifugation prove that all methyl methacrylate does not have polymerism and takes place.
Comparative example 2
Except that not having nano titanium oxide (sharp ore deposit type) powder, other condition is identical with embodiment 3.React after 300 minutes, sediment-free produces, and thermogravimetic analysis (TGA) and super centrifugation prove that all the pyrroles does not have polymerism and takes place.
Comparative example 3
Except that not having nano titanium oxide (sharp ore deposit type) powder, other condition is identical with embodiment 4.React after 300 minutes, sediment-free produces, and thermogravimetic analysis (TGA) and super centrifugation prove that all vinyl acetate does not have polymerism and takes place.
Claims (9)
1, a kind of preparation method of polymer/inorganic nanometer composite material powder is characterized in that polymerization system consisting of by weight:
(1) photocatalytic Nano semiconductor powder 0.01-40%,
(2) Raolical polymerizable monomer 0.01-20%,
(3) reaction control agent 0.01-10%,
(4) dispersion agent: surplus;
Reaction control agent adopts the compound that contains the variable valence gold ion, its step is as follows: adopt optical radiation exciting light catalytic Nano semiconductor, the trigger monomer polymerization makes monomer in nano grain surface or nearly surf zone polymerization, forms the polymer/inorganic nanometer composite material powder.Preparation method of the present invention does not need to add radical initiator.
2, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 1 is characterized in that described irradiation light is that wavelength is the 300-400 nanometer.
3, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 1 is characterized in that said photocatalytic Nano semiconductor powder is an one of the following or several: sharp ore deposit type titanium oxide, ferric oxide, silver suboxide, cupric oxide, Tungsten oxide 99.999, zinc oxide, stannic oxide, silicon oxide, cobalt oxide, aluminum oxide, magnesium oxide or fluorine doped tin oxide.
4, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 1, the particle diameter that it is characterized in that said photocatalytic Nano semiconductor powder are 10 nanometers-100 nanometers.
5, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 1 is characterized in that the reaction monomers of said radical polymerization contains one or more pairs key, and its structural formula is:
Wherein, R
1, R
2, R
3, R
4For straight chain, side chain or the cyclic saturated hydrocarbyl or the unsaturated alkyl of hydrogen or replacement arbitrarily, perhaps be amino, alkoxyl group, ketone group, amido or cyano group.
6, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 5,100 gram water dissolution 0.1-10 gram monomers when the water solubility that it is characterized in that the reaction monomers of said monomer radical polymerization is 20 ℃.
7, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 5,100 gram water dissolution 0-10 gram polymkeric substance when the water solubility that it is characterized in that said monomer homopolymer is 20 ℃.
8, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 1 is characterized in that said variable valence metal ion is Cu
2+, Fe
2+, Fe
3+Or Ag
+A kind of or its mixture.
9, the method for preparing the polymer/inorganic nanometer composite material powder according to claim 1 is characterized in that said polymerization system after mixing at least 5 minutes, starts ultraviolet source, in polymerization process, keeps whipped state.
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| CN 200410084568 CN1631907A (en) | 2004-11-25 | 2004-11-25 | Method for preparing polymer/inorganic nano composite material powder initiated by nano semiconductor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980410A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Composition for 3D printing and preparation method and product thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
| CN103980591A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Electronic radiation crosslinked polymeric material for 3D printing, preparation method and product thereof |
| CN105590759A (en) * | 2014-10-23 | 2016-05-18 | 同济大学 | Method of preparing ionic liquid gel electrolyte by semiconductor through self-initiated polymerization |
| CN108822249A (en) * | 2018-07-17 | 2018-11-16 | 常州工程职业技术学院 | A kind of Organic-inorganic composite lotion for field of metal surface treatment |
| CN109970897A (en) * | 2019-03-27 | 2019-07-05 | 中山大学 | Inorganic/polymer composite of one kind and preparation method thereof |
| CN110240670A (en) * | 2019-06-19 | 2019-09-17 | 河北科技大学 | A kind of preparation method of the polyacrylonitrile with spherical microscopic appearance |
| CN112521530A (en) * | 2020-11-24 | 2021-03-19 | 华南理工大学 | Composite inorganic photoinitiator using full spectrum and preparation method and application thereof |
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2004
- 2004-11-25 CN CN 200410084568 patent/CN1631907A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980410A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Composition for 3D printing and preparation method and product thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
| CN103980591A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Electronic radiation crosslinked polymeric material for 3D printing, preparation method and product thereof |
| CN103980592B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of high filler loading capacity micro nano powder/polymer composites for 3D printing and preparation method thereof and goods |
| CN103980410B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of composition and method of making the same for 3D printing and goods |
| CN103980591B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of electron radiation crosslinked polymeric materials for 3D printing and preparation method thereof and goods |
| CN105590759A (en) * | 2014-10-23 | 2016-05-18 | 同济大学 | Method of preparing ionic liquid gel electrolyte by semiconductor through self-initiated polymerization |
| CN105590759B (en) * | 2014-10-23 | 2018-06-26 | 同济大学 | A kind of method that semiconductor self-initiating polymerization prepares ionic liquid gel electrolyte |
| CN108822249A (en) * | 2018-07-17 | 2018-11-16 | 常州工程职业技术学院 | A kind of Organic-inorganic composite lotion for field of metal surface treatment |
| CN109970897A (en) * | 2019-03-27 | 2019-07-05 | 中山大学 | Inorganic/polymer composite of one kind and preparation method thereof |
| CN110240670A (en) * | 2019-06-19 | 2019-09-17 | 河北科技大学 | A kind of preparation method of the polyacrylonitrile with spherical microscopic appearance |
| CN110240670B (en) * | 2019-06-19 | 2021-07-20 | 河北科技大学 | Preparation method of polyacrylonitrile with spherical micro-morphology |
| CN112521530A (en) * | 2020-11-24 | 2021-03-19 | 华南理工大学 | Composite inorganic photoinitiator using full spectrum and preparation method and application thereof |
| CN112521530B (en) * | 2020-11-24 | 2021-09-21 | 华南理工大学 | Composite inorganic photoinitiator using full spectrum and preparation method and application thereof |
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